Multiple microlayer coextrusion of optical end products

ABSTRACT

The disclosed embodiments generally relate to extruding multiple layers of micro- to nano-polymer layers in a tubular shape. In particular, the aspects of the disclosed embodiments are directed to a method for producing a Bragg reflector comprising co-extrusion of micro- to nano-polymer layers in a tubular shape.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to and the benefit of U.S.patent application Ser. No. 15/477,252 filed Apr. 3, 2017 which issuedas U.S. Pat. No. 10,029,431 and Ser. No. 13/972,753 filed Aug. 21, 2013which issued as U.S. Pat. No. 9,643,368 and U.S. Provisional Application61/691,771 filed Aug. 21, 2012, the disclosures of which areincorporated herein by reference in their entireties.

FIELD

The disclosed embodiments generally relate to extruding multiple layersof micro- to nano- polymer layers in a tubular shape.

BACKGROUND

Multilayer coextrusion offers many unique design possibilities in theworld of plastics. There are many established technologies for thecreation of flat films with tens to thousands of layers. Suchtechnologies generally utilize a feed-block which will either create thelayers of polymer through layer by layer addition, create a layerpattern and then multiply it through a layer multiplication technique,or through some combination of the two. Some methods to create a tubularproduct from a stream of layers include, wrapping the stream annularlyinto a tube or tubular shape or by combining the stream along with otherstreams into the desired shape. One such micro-layer extrusion processmethod that provides products with small grain features is as describedin U.S. Pat. No. 7,690,908, (hereinafter the “'908 Patent”). Anotherexample of a device that can be used in a microlayer extrusion processto create a laminated output with dimensions in the micro and nanometerrange is United States Patent Publication 2012/0189789 (hereinafter the“789 Publication”) published Jul. 26, 2012, entitled “Method andApparatus for Forming High Strength Products,” the disclosure of whichis incorporated herein by reference in its entirety. This nano-flow diedevice (referred to herein as the “nano-flow die”) can be used to createlayers in a multi-layered product that have at least one dimension inthe nanometer range. Multilayered head extrusion die assemblers affordadditional methods to make tubular products such as those described inU.S. Non-Provisional Application 61/639,034. In one such embodiment, themulti-layer extrusion die assembly includes a body, a main boreextending longitudinally through the assembly, a core tube, and aplurality of dies. The extrusion die assembly is configured to receivean input stream of material and divide the input stream into a pluralityof material streams. Other methods of extrusion yield productspossessing electrical properties such as described in U.S.Non-Provisional application Ser. No. 13/916,551, filed Jun. 12, 2013.More specifically, these extrusion products contain thin layer(s)(milli, micro or nano) wherein one or more layers contain electricalconducting materials and more specifically nanoparticle electricalconducting materials. Yet other methods of producing products with manylayers include folding techniques of flows already in a tubular shapesuch as described in U.S. Provisional Application 61/728,213 filed Nov.19, 2012.

Each of the above Applications, Publications or Patents is commonlyowned by the assignee of the instant application, and the disclosures ofwhich are incorporated herein by reference in their entirety.

SUMMARY

The present disclosure relates to the production of a Bragg reflectorusing multilayered co-extrusion of micro- to nano- polymer layers in atubular shape. Such tubular shapes may be of variable length andconstruction. Certain tubular shapes may contain a core (which may besubstantive or hollow). When the core is substantive it may comprisegases, liquids or solids. Suitable solids include polymeric materials ormatter which is coextruded with the multilayer tube. Such polymericmaterials may be transmissible to incident light. Suitable liquidsinclude water, alcohols and organic liquids.

A Bragg reflector or Bragg fiber can be produced from multilayeredco-extrusion technology. Alternating layers of polymeric material form awaveguide that allows the transmittance of electromagnetic waves.Waveguides are used in a variety of applications, specifically lasers,sensors, and optical fibers. A Bragg reflector can be used to amplifythe total internal reflection of a solid optical fiber or be used in ahollow optical fiber to provide the internal reflection.

A Bragg reflector works on the principles of reflection, refraction, andconstructive interference.

Alternating layers may be of constant, variable or Chirped gradientthickness. Layers ¼ the wavelength of incident light will constructivelymagnify the incident light. Materials with different refractive indicesare layered to produce a Bragg reflector. Light reflects and refractsfrom each layer interface. By alternating materials of high and lowrefractive indexes in layers ¼ the wavelength of incident light, thereflected light will constructively interfere with the reflected lightfrom previous layers, amplifying the reflection.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph illustrating the interference occurring at each layerof the

Bragg reflector.

FIGS. 2a and 2b are illustrations of different thickness layers ofpolymeric materials.

FIGS. 3a and 3b illustrate different examples of cross-sectionalgeometries.

FIG. 4 illustrates an outer layer applied around the alternating layers.

FIGS. 5a and 5b illustrate examples of chirped layers and constantlayers.

FIG. 6 illustrates a single interface between the cladding and the core.

FIG. 7 illustrates an exemplary product with annular layers with onelayer having a graded refractive index.

FIG. 8 illustrates a waveguide with multilayer cladding around a corealong with a separate outer cladding.

FIGS. 9(a)-9(g) illustrate cores of different cross-sections.

FIG. 10 illustrate a rod that can be extruded.

FIG. 11 illustrates a stream of layers made to form a tube.

FIG. 12 illustrates transmitting light to of from a center of thecross-section.

FIG. 13(a) illustrates an example of a stream of material that could beformed by layering a stream containing alternating layers of black andwhite material with a stream of the black material.

FIG. 13(b) illustrates streams of alternating layers combined onto asmall cord and combined with an outside coating.

FIG. 1 depicts the interference that occurs at each layer of the Braggreflector. The constructive interference occurs when the layer thickness(d) is ¼ the wavelength of the incident wave. Alternating layers ofpolymeric materials with different refractive indices can be used as aBragg reflector, suitable polymers include PMMA (poly(methylmethacrylate)), PS (polystyrene), polypropylene, polycarbonate,poly(2-chlorostyrene), poly(2,6-dichlorostyrene),poly(2,6-dichlorostyrene-co-glycidyl methacrylate), poly(1-naphthylmethacrylate), poly(pentabromobenzyl acrylate), poly(pentabromobenzylmethacrylate), poly(2,4,6-tribromophenyl methacrylate-co-glycidylmethacrylate), poly(vinyl phenyl sulfide), poly(N-vinylphthalimide),poly(2-vinylthiophene), and cyclic polyolefines including deuterated orfluorinated analogs, preferably polymethyl methacrylate and polystyrene.

Increasing the refractive index difference of the layers and number oflayers increases the reflectivity and widens the reflected bandwidth.Additionally, layers can be of constant thickness, such as depicted inFIG. 2 a, variable thickness or a Chirped gradient such as depicted inFIG. 2 b. Chirped gradients generally refers to a linear variation inthe thickness of the grating layers and as such will increase the rangeof reflected wavelengths.

As seen in the cross sectional geometries of FIGS. 3a and 3 b, theselayers can be formed around a core (3 b) or may be hollow (3 a). Thecore may be comprised of any suitable material including objects (suchas wires, rods, chains, fibers, etc.) in which the layers are extrudedaround the object or the core may comprise alternative polymericmaterials.

An outer layer (or outer cladding, see also FIG. 8 below) can also beapplied around the alternating layers, as illustrated in FIG. 4.

These geometries can be used to make waveguides, optical fibers andBragg fibers. These in turn can be used in applications includinglasers, fiber optics, lenses, solar fibers, circuits, switches,information transmission and sensors.

Two Bragg gratings can also be applied around an inner layer in order totransmit the wave inside this layer. This geometry is illustrated inFIG. 5, both with chirped layers (5 a) and constant layers (5 b). Thesegeometries may be used to make annular Bragg resonators.

In another embodiment of the present disclosure, multiple layerco-extrusion in a tubular shape may be used for the production ofoptical fibers. Optical Fibers are generally made with a cladding and acore. Many do not rely on Bragg reflection but rely on total internalreflection based on the single interface between the cladding and thecore, as depicted in FIG. 6. However, an optical fiber can be made touse constructive interference from multilayered Bragg cladding in orderto transmit the wave down the optical fiber.

FIG. 7 demonstrates a product with annular layers in which one of thealternating layering has a graded refractive index. In this example thegradient is present in every other layer but could be present inconsecutive layers. The gradient need not be linear but could take otherforms such as parabolic.

Changing the refractive index can also effect the dispersion performanceof an optical fiber. Microlayers with a gradient refractive index canalso be used to create lenses.

In another embodiment of the invention multi-layer co-extrusion in atubular shape may be used in the production of lasers. A laser utilizingthe reflective properties of the multilayer Bragg grating would consistof a core bordered on each side by Bragg layers. A gain material, usedin lasers to amplify light, would be added to the Bragg cladding or thecore, resulting in a reflection greater than unity.

FIG. 8 refers to a waveguide with a multilayer cladding around a corealong with a separate outer cladding.

The present invention also relates to tubes comprising an optical fibercoated with a photovoltaic material. Beyond annular layers, multiplestreams of layered material(s) and non-layered-material(s) can bemerged, folded and/or bent prior to extrusion in different orientationsto create cross-sections which have unique properties and functions. Thecross-sections of the resultant product could be any shape such asrectangular or elliptical and may or may not contain a core or behollow. Some of such cross sections are depicted in FIGS. 9(a)-9(g).

In another embodiment, the multi-stream approach may be used to createproducts which will have an increased surface area. As illustrated inFIG. 9(a), streams of alternating layers of materials can be separatedby ‘stems’ comprised of a single material or mixture and applied onto acore. Each stem can be made of its own respective material or mixtureallowing for the properties desired in that stem. A material or mixturemay then be removed by some process, whether it is mechanical in naturesuch as peeling or chemical in nature such as dissolving. If one of thematerials or mixtures used in the stem along with one or more of thematerials used in the layers can all be removed, the result would be acore with stems protruding from the surface. These stems would havebranches (layers) attached with a large surface area exposed to theenvironment. In the FIG. 9(a) there are alternating layers of grey andblack material separated by alternating grey and black stems. Only sixlayers are shown in each ‘stream’ for illustrative purposes but cancomprise of thousands of layers. If all the black material were removed,the result would be a grey core with four stems each with six branchesof material. This greatly increases the surface area exposed to theenvironment.

In the embodiment of FIG. 9(b), the stems are tapered radially inwards.The stems can also be made to be tapered radially outwards. The stemsand branches can all be made to have different thicknesses and there maybe any number of each.

In the embodiment of FIG. 9(c), the core is comprised of a tube made ofthe grey material. Examples of a core include a solid rod, a hollowtube, a wire, or a profile all of which can either be coextruded orextruded onto and can be comprised of any materials with or withoutlayers. The core can also be absent.

In the embodiment of FIG. 9(d), a layer of black material is coextrudedon the outside of the product. This outer layer can be composed ofmultiple layers and can be comprised of any suitable material ormaterials.

A product could also be configured as seen in FIG. 9(e) where there is asingle layer of material between the stems or multiple layers of thesame material.

Multiple layers of streams and stems can also be used to be used to beable to create geometries like the one illustrated in FIG. 9(f). Theseslayers can contain different numbers of layers, streams and stems indifferent orientations.

The branch and stem approach may also be applied to streams of rotatedor vertical layers to create many stems such as depicted in FIG. 9(g)

The geometries illustrated in FIGS. 9(a-g) are useful in applicationswhere the surface area contact between two materials is important suchas an optical fiber coated with a photovoltaic material (such as a dyedzinc-oxide for photon capture) rather than its cladding to create asolar fiber. Another application could be time varying drug delivery.

Beyond designing a waveguide in the direction of extrusion, pathwayscould also be designed to travel across the extruded cross-section. FIG.10 depicts a rod which could be extruded. This cross section can be madeby merging multiple streams together prior to extrusions. Each one ofthese streams could be made in their own way; such as through creatinglayers and bending them, or through merging multiple other streams. Sucha cross section would provide a waveguide pathway for light to traveland turn or form some juncture. There could be any number of inlets andoutlets for the light to travel.

A stream of layers could also be made to form a tube through a wrappingprocess which could occur internally prior to extrusion or externallyafter extrusion (see FIG. 11). This geometry which could wrap around anynumber of times, would bring light either from inside of the geometry tothe outside of the geometry or the reverse.

Another approach to transmit light to or from the center of thecross-section is depicted in FIG. 12.

FIG. 13(a) represents an example of a stream of material that could beformed by layering a stream containing alternating layers of black andwhite material with a stream of the black material. Three streamsanalogous to the method described above may be combined onto a smallcore containing the black material and then combined with an outsidecoating to form the cross section 13(b). This example cross sectioncould be used to create photonic crystal wave guides. These waveguidesuse holes in a cladding material to guide a wave along a path. Photoniccrystal wave guides have numerous uses including photonic crystal fibersand lasers. The white material in the figures above could be dissolvedto create holes or contain a material with different refractive indicesfrom the black material.

All these geometries, methods and products may also be used inconjunction with 3D printing methods in which the extrusion head iscoupled to the 3D printing mechanism so as to extrude the geometriesdescribed above. Examples could include 3D printed optical fibers,waveguides or Annular Bragg Resonators.

All figures contain a limited number of layers for illustration purposesbut could range from under 10 to thousands of layers.

1-30. (canceled)
 31. A tubular device comprising multiple streams thatare merged, folded, bent or wrapped and forming radial stems orbranches. 32-35. (canceled)
 36. A tubular device according to claim 31,wherein said stems are tapered radially inwards.
 37. A tubular deviceaccording to claim 31, wherein said stems are tapered radially outwards.38. A tubular device according to claim 31, wherein the stems haveconstant thicknesses.
 39. A tubular device according to claim 31,wherein the stems have different thicknesses.
 40. A tubular deviceaccording to claim 31, wherein said coated optical fiber is a photoniccrystal fiber.
 41. A tubular device according to claim 31, wherein saidcoated fiber bends light.
 42. A tubular device according to claim 31,wherein said coated fiber transmits light through a tube.